Process for fast dyeing of fibres and shaped articles

ABSTRACT

FIBERS OR SHAPED ARTICLES MADE FROM FIBERS OF HYDROPHOBIC POLYMERIC HYDROCARBON, CHLORINATED POLYMERIC HYDROCARBON OR POLYESTER WHICH DO NOT CONTAIN A POLAR GROUP BUT WHICH DO CONTAIN A METHYL, METHYLENE OR METHINE GROUP OR A BENZENE NUCLEUS MAY BE FAST DYED BY DYEING THE FIBERS OR SHAPED ARTICLES WITH DYESTUFF CONTAINING A SULFON AZIDE GROUP BY A CONVENTIONAL DYEING PROCESS, TREATING THE DYED ARTICLE TO DECOMPOSE THE SULFON AZIDE TO SULFONYL NITRENE WHICH FORMS A COVALENT BOND WITH THE FIBER AND WASHING THE FAST DYED FIBER TO REMOVE THE EXCESS DYESTUFF.

United States Patent 3,695,821 PROCESS FOR FAST DYEING 0F FIBRES AND SHAPED ARTICLES Nobuhiko Kuroki, Sakai, Kiroku Komatsu, Higashiosaka, Shuji Tamura, Kishiwada, and Hiroyuki Matsumoto, Yono, Japan, assignors to Nippon Kayaku Kabushiki Kaisha, Tokyo, Japan No Drawing. Filed Nov. 18, 1970, Ser. No. 90,873 Claims priority, applicatiorglipan, Nov. 22, 1969,

Int. (:1. D66 1 3/10 US. Cl. 8-2 4 Claims ABSTRACT OF THE DISCLOSURE DETAHJED DESCRIPTION OF THE INVENTION The present invention relates to a process for fast dyeing of polymeric hydrocarbon, chlorinated polymeric hydrocarbon or polyester fibres or their shaped articles.

When dyeing polyester fibres, for example, they are usually dyed in a dispersion by high-pressure dyeing, carrier dyeing, or thermosol dyeing, but in these processes, fastness to sublimation is often unsatisfactory depending on the structure of the dyestulf.

However, fastness to sublimation and other fastness might be improved, if a dyestuff possessing a reactive group is used to react with fibres and to form a covalent bond, as conventional reactive dyestuffs are. The present inventors have noticed a methyl group (or a methylene group) or a benzene nucleus in a molecule of polyester or polypropylene fibres, and supposed that the fibres must be dyed with good fastness by a dyestulf having a reactive group reacting with said group or nucleus: after earnest researches, the present inventors have found that hydrophobic fibres without a reactive polar group can be dyed with good fastness by forming a dyestulf containing a sulfon azide group (-SO N on said fibres and then exposing those fibres to heat, steam or ultraviolet rays.

As the dyestulf which can be used according to the process of this invention, there are exemplified azo dyestuffs having a sulfon azide group in a molecule, anthraquinone dyestuffs, quinoline dyestuffs, methine dyestuffs, diphenylamine dyestuffs, indigoid dyestuffs, and nitro dyestuffs.

A process, in which a dyestutf containing a sulfonazide group is allowed to react with fibres having a so-called reactive group such as -OH group and NH group, for example, cellulose fibres, acetate fibres and polyamide fibres, is found in Japanese patent publication No. 19233/ 1961. The so-called reactive groups of this patent are also polar groups. In the process of the present invention, however, dyed articles with good fastness is obtained by forming a covalent bond as allowing sulfonyl nitrene (-SOgN) produced by thermal decomposition or photolysis of a sulfon azide group to attack a methyl group (or a methylene or methine group) or a benzene nucleus in fibres possessing a reactive group but no polar group such as polyester fibres and polypropylene fibres, their shaped articles or polyethylene shaped articles. The reaction mechanism for the decomposition of sulfon azide and 3,695,821 Patented Oct. 3, 1972 the attack of sulfonyl nitrene on a methyl group or a benzene nucleus is discussed by L. Homer and A. Christmann in Angewandte Chemie, 75. Jahrgang 1963, Nr. 15, PP. 707-16.

The process of this invention is substantially dilferent from the process of Japanese patent publication No. 19233/1961 wherein a dyestutf reacts with a reactive polar group in a fibre from the standpoint of the reaction mechanism, and it is an absolutely novel process for dyeing. V

The gist of the present invention is that polymeric hydrocarbon, chlorinated polymeric hydrocarbon or polyester fibres or their shaped articles (for example, film, sheet, etc.) are dyed with a dyestuif having a general formula,

'D-(SO;,,;N (wherein D=chromogen, n=q positive integer) by a conventional dyeing process, such as highpressure dyeing, carrier dyeing, and thermosol dyeing, and then they are exposed to heat, steam or ultraviolet rays at a temperature from 12.0 to 220 C. In thermosol dyeing, a good result is obtained by a usually employed process, and it is no need to repeat heat treatment and other treatment.

In said process, a sulfon azide group attacks a carbon atom in a methyl group (or a methylene or methine group) or a benzene nucleus to react via a sulfonylnitrene intermediate and a nitrogen-carbon bond is accomplished, as described previously.

The dyed articles thus obtained is further treated with an organic solvent and/or soaped to remove the unreacted dyestuff, and then water-washed and dried.

The dyed articles thus obtained have excellent fastness, and particularly, fastness to sublimation is so excellent as bleeding on the attached cloth (of polyester) is 4.5-5 class in the test performed at 2.00 C. for 1 minute.

-As the fibres and shaped articles to be employed in the present invention, there are exemplified polyester, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, and chlorinated polyethylene.

The dyestuif having a sulfon azide group used in this invention is manufactured by the following method: a dyestutf is chlorosulfonated by a conventional method to introduce a sulfonyl chloride group, and the obtained chlorosulfonate is allowed to react with sodium azide to form a sulfon azide group.

It is also possible to allow hydrozine hydrate or hydrazine to react with said chlorosulfonate to form a sulfon hydrozide group with which sodium nitritereacts to form a sulfon azide group.

Alternatively, a dyestulf having: a sulfonic acid group (or an intermediate containing a sulfonic acid group for forming such a dyestuff) is converted to sulfon halogenide by a usual method, and sulfon azide group is formed by the above-described method.

As to azo dyestufis, when using an amino compound having a sulfon halogenide group as a diazo component, after forming a sulfon hydrozide group, a sulfon hydrozide group is converted to azide simultaneously to diazotization of an amine group by treating with nitrite and an acid.

The invention is explained more concretely as referring examples, in which parts are all by weight.

Example 1 In a dyebath prepared by adding to 4000 parts of water containing 1 part of sodium oleylsulfate a dispersion produced by grinding 1.5 part of a dyestutf represented by the following Formula I 1.5 parts of a condensate of alkylnaphthaline sulfonic acid as a dispersing agent and 0.7 part of sodium polyalkylnaphthaline sulfonate as a wetting agent together with water for a several hours, 100 parts of polyester fibre (for example, Tetron cloth) were immersed and dyed in a pressure container at 130 C. for 60 minutes. After water-washing the dyed fibre, it was treated at 160 C. for 30 minutes: it was immersed in N,N-dimethylformic amide at room temperature or an elevated temperature to remove completely the unreacted dyestutf, and then it was soaped, water-washed and dried to produce a fast dyed article, particularly an orange yellow dyed article having excellent fastness to sublimation.

Fastness to sublimation (200 C., 1 min.)

Alteration in colour: 4.5-5 class Bleeding on Tetron: 4.5-5 class Fastness to sublimation obtained by high-pressure dyeing without heat treatment was so poor as shown below.

Fastness to sublimation (200 C., 1 min.)

Alteration in colour: 1 class (brown change) Bleeding on Tetron: 1 class Example 2 1.5 part of a dyestuff represented by the following general Formula II,

was dispersed and high-pressure dyeing, heat treatment and treatment with N,N-dimethylformic amide were performed, as similar in Example 1: thus, there was obtained a fast dyed article, particularly a clear bluish red polyester dyed article having excellent fastness to sublimation.

Fastness to sublimation (200 C., 1 min.)

Alteration in colour: class Bleeding on Tetron: 4.5-5 class The used dyestnff (H) was prepared as follows: 9.9 parts of 1-amino2-phenoxy-4-hydroxy-anthraquinone synthesized by a publicly-known process were added to 75 parts of chlorosulfonic acid as cooling, and after the reaction at temperatures lower than 100 C., the reaction mixture was poured into ice to separate a crystal, which was filtered, and washed with iced water: then, the obtained chlorosulfona-te was dissolved in 60 parts of formic amide, and allowed to react at 70-80 C. as adding a solution consisting of 3 parts of sodium azide and 30 parts of water: then, separated crystal was filtered, water-washed and dried.

Example 3 1.5 parts of a dyestutf represented by the following Formula III:

was dispersed by the same method as described in Example l: in a dyebath consisting of said dispersion, 5 parts of a commercially available carrier (Carriant 323, manufactured by Toho Kagaku Co.) and 1500 parts of water, 100 parts of Tetron fabric was immersed. The dyebath was heated up to the boiling point within 30 minutes and the temperature was maintained for 60 minutes. The dyed article was water-washed, treated at 160 C. for

4 30 minutes, and then immersed in N,N-dimethylformic amide: after extracting and removing the unreacted dycstuff at room temperature or an elevated temperature, it was soaped, water-washed and dried: thus, there was obtained a fast dyed article, particularly a clear yellow dyed article having excellent fastness to sublimation.

Fastness to sublimation (200 C., 1 min.)

Alteration in colour: 4.5-5 class Bleeding on Tetron: 4.5-5 class The used methine dyestulf (III) was prepared as follows: 16 parts of 1-(benzene-4-sodium sulfonate)-3- methyl-S-pyrazolone and 9 parts of 4-N,N-dimethylaminobenzaldehyde were allowed to react with each other in the presence of a catalytic amount of glacial acetic acid in 200 parts of methanol for 2 hours at the boiling point; after cooling, the separated crystal was filtered and dried sufiiciently. 16 parts of the dyestuff was suspended in 160 parts of chlorobenzene, and after adding 3.2 parts of N,N-dimethylformic amide and 7.2 parts of thionylchloride, reaction was carried out at C. for

1 hour; after cooling with ice, the obtained crystal was filtered and allowed to react with sodium amide by the same method for manufacturing the dyestutf (II) used in Example 1.

The dyestufi (III) may be prepared by the reaction with hydrazine hydrate at 25 C. after converting to chlorosulfonate, and after converting to sulfonic hydrazide, adding an aqueous solution of sodium nitrite to convert to azide.

Example 4 1.5 part of a dyestuff represented by the following general Formula IV:

Hs V) Quite the same process can be applied to dyeing of polypropylene film instead of polypropylene fibres, and a good result can be obtained.

The used azo dyestuff (IV) was prepared as follows: 14 parts of 4-amino-phenyl-sulfonic hydrazide were dissolved in a solution consisting of 45 parts of concentrated hydrochloric acid and 200 parts of water, and as cooling at temperatures lower than 5 C., a solution consisting of 11 parts of sodium nitrite and parts of water was dripped: reaction was performed for 1 hour at temperatures lower than 10 C. to form diazo and diazide and then added gradually to a solution consisting of 12 parts of N,N-diethyl-m-toluidine and 200 parts of methanol as cooling. Coupling was performed at 10-15 C. and the separated crystal was filtered and dried in vacuum.

Example 5 1.5 parts of a dyestutf represented by the following general Formula V:

was treated similarly as described in Example 1 to prepare a dyebath, in which 100 parts of polyester film were Example 6 1.5 parts of a dyestuif (VI) represented by the following general Formula VI:

was treated similarly as described in Example 1 to prepare a dyebath, in which 100 parts of polypropylene film were immersed: after keeping them in the dyebath at 100 C. for 90 minutes, they were water-washed. Then, the dye film was exposed to ultraviolet rays by means of a high-pressure mercury lamp for 15 minutes at room temperature. The unreacted dyestuff' was extracted in trichloroethylene at room temperature, and the film was water-washed to obtain yellow dyed polypropylene film.

The used dyestulf (V) was prepared similarly to the dyestuff (IV), except that 4-amino-3-chlorophenyl-sulfonic hydrazide was used instead of 4-aminophenyl-su1- fonic hydrazide and N,N-dimethylaniline instead of N,N diethyl-m-toluidine.

Example 7 Using each 1.5 part of the dyestuffs shown by the following Formulae VII-XXVII, polyester fibres were dyed by the same method as described in Example 1, and there could be obtained fast dyed articles having the hue shown in the right side, particularly dyed articles having excellent fastness to sublimation.

Hue of 01 Dyestufi ester fib r e y /CH; (VII) Yellow.

C boa,

/ 2Hs (VIII) Orange.

C H O 1 1 2 a H /C:Hs (IX) D0.

CzHOCOCH 2H; (X) Orangecameo-G /C3H5 (XI) Orange.

021140 0 0 0 CrHB 2 5 (XII) D0.

CzHrNHCO- XIII Y ll W1 11- NzOzS-N=N-NHC:H OH grgwfi.

/C1Hs (XIV) Orarfige- N:OzS-N=N -N\ W C H CN 2 (H1 (XV) Yellow. Ns 2s-N=N (XVI) Yellowish- N 0: S -N= -N=N 0 H orange.

H (XVII) Red;

Hue of polyester fibre Dyestuff (XVIII) Red.

S OzNI m Tb G m m 0 S H H N N 0 S OgNl (XXII) Blue.

xxm

S OzNa (XXIV) Red.

(XXV) Yellow.

Hue of poly- Dyestufi ester fibre N (XXVI) Yellowishorange.

SOzN: r m, xxvn) Yellow. our-@mr-Qs 01m We claim: the fibers or shaped article are decomposed during the 1. A process for fast dyeing polymeric hydrocarbon, chlorinated polymeric hydrocarbon or polyester fibers which do not contain a polar group but which do contain at least one of the following: a methyl, methylene, or methine group or a benzene nucleus, or a shaped article made from such fibers comprising: dyeing the fibers or shaped articles with a dyestuff containing a sulfon azide group; exposing the dyestufl molecules attached to the fibers or shaped article to heat, steam or ultra-violet rays to a degree and for a length of time sufficient to decompose the sulfon azide to sulfonyl nitrene, which then forms a covalent bond to the methyl, methylene or methine group, or the benzene nucleus of the fibers or shaped article.

2. The fast dyeing process of claim 1, wherein the sulfon azide groups of the dyestulf molecules attached to the fibers or shaped article are decomposed by heating the fibers or shaped article after the completion of the dyeing process at a temperature from 120-220 C.

3. The fast dyeing process of claim 1, wherein the sulfon azide groups of the dyestufi molecules attached to dyeing step by use of thermosol dyeing.

4. The fast dyeing process of claim 1, wherein the sulfon azide groups of the dyestutf molecules attached to the fibers or shaped article are decomposed by exposing the fibers or shaped article after completion of the dyeing process to ultraviolet radiation.

References Cited FOREIGN PATENTS 3,619,233 1961 Japan 8-4 OTHER REFERENCES Homer et al., Angewandte Chemie, 75, January 1963, pp. 70716.

GEORGE F. LESMES, Primary Examiner J. T. BRAMMER, Assistant Examiner US. Cl. X.R. 

